I 


I 


\ 


\ 


/ 


THE  PREPARATION  OP" 
PARA-PHENOXY-PHENYL-ARSONIC  ACID 


BY 


SEYMOUR  HOUGHTON  COOK. 


THESIS 


FOR  THE 


DEGREE  OF  BACHELOR  OF  SCIENCE 

in 


CHEMICAL  ENGINEERING 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 


UNIVERSITY  OF  ILLINOIS 


1921 


o/n 


UNIVERSITY  OF  ILLINOIS 


Uf 

CO 


i92_i. 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 

.SBmQUE._lLQUilHTmi_ilQM. 

ENTITLED THP  PREPARATION  OR  PARA-PH?,N QAY-PIia^YL~ARAQl.LlCL 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 


DEGREE  OF 3ax^Jsiox_a£_^cJLeiia£.-lii_XItieiniiiaX-J 


HEAD  OF  DEPARTMENT  OF CI^ISTRY 


49 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/preparationofparOOcook 


FQ-iSWORD . 

It  is  with  great  pleasure  and  sincere  respect 
that  the  writer  of  this  paper  takes  this  opportunity 
of  expressing  his  full  appreciation  of  the  cooperat- 
ion and  guidance  afforded  him  "by  Dr.  Doger  Adams  in 
the  suggestion  and  prosecution  of  this  investigation. 


. 


ITABES  OF  CQirTlulI^o , 

Sub.icc  t.  Pace . 

Introduction  . 1 

Historical  2 

Experimental  

Sodium  Phenolate 5 

~ -nitro-chlorbenzene 6 

Mono-nitro-diphenyl  ether  from  sodium  phenol- 

ate  and  p-nitro-chlorbenzene  8 

Mono-nitro-diphenyl  ether  from  potassium  phen 

olate  and  p-nitro-brombenzene '10 

Mono -amino -diphenyl  ether — 12 

Par a-phenoxy-phenyl-ar sonic  acid  13 

* 

Summary ■ ■ 14 

References 16 

Mote:  -umbers  within  brackets,  i.e.  lid),  refer  to 

references  on  page  sixteen. 


mono -nitro- diphenyl  ethers  and  their  derivatives ( 14 ) , and  it  was 
thought  best  to  try  out  their  method  of  preparation  in  the  product- 
ion of  the  mono-nitro  derivative  to  he  used  in  this  work,  Some  of 
the  results  obtained  by  the  writer  were  not  at  all  in  agreement  with 
those  obtained  by  the  investigators  referred  to  above.  It  is  with 
a view  to  throwing  further  light  upon  the  phenomena  observed  in  the 
preparation  of  this  compound,  that  the  experimental  work  carried  out 
by  the  writer  will  be  reviewed  in  detail. 

Historical . 

The  method  employed  in  the  work  undertaken  in 
this  problem,  for  introducing  the  arsenic  acid  group  into  the  ben- 
zene nucleus  is  not  a new  one,  but  one  that  has  found  extensive  ap- 
plication in  the  preparation  of  similar  organic  arsenical  compounds. 
It  involves  the  replacement  of  the  diazonium  grouping  with  the  ar- 
senic acid  group  by  means  of  running  the  water  solution  of  the  diaz- 
oniun  salt  into  a sodium  carbonate  solution  of  arsenious  oxide  at  a 
temperature  of  from  0°G.  to  15°C.  in  the  presence  of  copper  sulfate 
which  acts  as  a catalyst.  Nitrogen  is  evolved  and  sodium  chloride 
is  formed  at  the  same  time  that  the  arsenic  acid  grouping  enters  the 
ring  nucleus. 

Some  of  the  earlier  methods  employed  for  the  re- 
placement of  the  diazo  grouping  have  differed  in  their  detail  from 
this  general  method,  but  where  ever  a catalyst  has  been  employed,  it 
has  been  found  that  copper,  silver,  nickel,  or  cobalt,  as  well  as 
their  salts  facilitate  the  removal  of  the  diazo  nitrogen  at  low  temp- 
eratures, and  obviate  the  formation  of  byproducts (l6 ) • 

In  the  preparation  of  3*. 5-dichlorophenyl-arsenic 


a 


-o- 


acid,  3:  5-aichlor-p-arsanilic  acid  was  diazotized  by  Morgan  accord- 
ing to  Witt's  process(l).  The  clear  cold  nitric  acid  solution  of 
the  diazotized  compound  was  mixed  with  alcohol  and  a srn,  11  amount  of 
finely  divided  copper.  Effervescence  set  in  at  the  temperature  of 
ice,  and  was  completed  by  gentle  heating.  The  copper  was  complete- 
ly dissolved,  and  the  solution  was  again  cooled.  The  3:5-dichlor- 
phenyl-arsenic  acid  separated  out  in  crystals. 

Many  other  aromatic  arsenic als  have  been  x>re- 
pared  in  a similar  manner.  Among  the  most  important  of  these  are 
those  which  are  briefly  mentioned  below: 

T-phenylene-diarsenic-acid  has  been  perpared(s) 
by  the  diazotization  of  sodium-p-arsanilate , and  warming  the  diazo- 
tized solution  with  sodium  arsenite  without  a catalyst. 

P-phen-phenyl-arsenic  acid  v/as  prepared  by  Bit- 
termann(io),  by  the  use  of  Bart's  reaction  for  replacing  the  diazo- 
niurn  group  with  the  arsenic  acid  group. 

Phenyl-acetic-p-arsonic  acid  was  prepared- by  Gr. 
A.  Hobertson  and  J.  Stieglitz  from  p-amino-phen-acetic  acid(ll). 

Phenol -p-arsenic  acid  has  been  prepared  by  Mor- 
gan from  p-amino-phenol  by  Part's  reaction  without  a catalyst,  but 
with  a slight  application  of  heat (2). 

2 :4-dinitro-arsenic~ acid  has  been  prepared  by 
Morgan  from  2:4-dinitro-aniline (2 ) . The  best  yields  were  obtained 
with  an  excess  of  acid  in  place  of  with  a neutral  or  alkaline  sol- 
ution of  sodium  arsenite. 

3- nitro-4-hydroxy-phenyl-arsenic  acid  has  been 
prepared  by  Morgan  from  o-nitro-p- .mino-phenol (2 ) . 

4- nitro-2-hydroxy-phenyl-arsenic  acid  was  also 


-4- 


prepared  by  Morgan  iro.:.  4-nitro-2-a  o -phenol  by  Bart’s  reaction 

with  alkaline  sodium  arsenitefs). 

3- amino-phenol-6-arsenic  acid  was  prepared  by 
Morgan  from  3-nitro  6- amino -phenol  and  subsequent  reduc tion( 2 ) . 

Jacobs,  Heidelberger , and  Molf  have  prepared  sev- 
eral nitro  and  amino  aryl  arsenic  acidsfd). 

Morgan  has  prepared  p-cv loro-phenyl-arsenic  acid  ; 
from  p-chloraniline f 2 ) . 

P-tolyl-arsenie  acid  has  been  prepared  by  Bart’s 
reaction  when  a solution  of  p-toluer.e-diasonium-chloride  is  treated 
with  a neutral  aqueous  solution  of  sodium  arsenitc,  and  the  mixture 
is  gently  warmed  to  evolve  the  nitrogen(2J. 

The  following  arsonic  acid  derivatives  of  anth- 
raquinone  have  been  prepared  by  I.  Benda(7). 

^nthraquinone-2-arsonic  a-cid. 

4- amino-anthraquinone-l-arsonic  acid  from  1:4- 
didmino-anthraquinone . 

4 : 8-dihydroxy-anthraquinone-l : 5-diarsonic  acid, 
from  1 : 5 -diamino- an thraquinone . 

In  addition  to  the  above  mentioned  preparations, 
A.  Schmidt,  Heysler,  and  Modebeul  have  done  considerable  work 

on  the  diazo  synthesis  of  aromatic  arsonic  acids,  and  have  shown 
their  theoretical  importance  in  relation  to  similar  reactions (9  )» 

a.  Mouneyart  also  has  done  considerable  work  up- 
on aromatic  arsonic  acids  obtained  by  the  reaction  of  aromatic  di- 
azo com  n is  upon  acid,  neutral,  and  alkaline  aqueous  and  alcoholic 
solutions  of  arsenious  ac.id  in  the  presence  of  copper  salts,  and  an 
appropriate  reducing  agent.  The  reducing  agents  used  most  generally 


for  an  acid  solution  are  HgPOg,  Na^POg^nd  KCit  or  CuOH;  for  neut- 
ral solutions  ^a2^2^4»  or  Sodium-formaldehydesulfoxalate ; Tor  al- 
kaline solutions  HCIIO  Hypo  sulfite,  or  formal ' 1' oxalate,  or 

Ha-  AsO’-  in  excessflS). 


Hicoerir.iciatal . 

The  final  product  of  this  investigation  was  pre- 
pared through  the  following  series  of  reactions; 

^ <7^0^  — > + /**c/ 

<d>  o/K  -h  * <0  c Y-  jnf&A 

. <^>-  v~<^>'/YBA/  +-^<*3  '4*0?  — > ^ 

. 0-^0  *2sVb<?/ 


?re  .^ration  of  -odium  Pi. 


it  was  first  necessary  to  prepare  sodium  phenol - 
ate,  and  p-nitro-chior-benzene.  Three  methods  were  employed  in  the 
preparation  of  the  former  compound.  The  last  method  proved  to  he 
the  most  satisfactory*  The  first  method  consisted  in  dissolving 

50  grams  of  solid  sodium  hydroxide  in  about  400  cc.  of  distilled  wat- 
er, and  adding  100  grams  of  phenol*  The  solution  was  evaporated  to 
dryness,  and  the  very  hard  residue  broken  up,  and  used  in  the  sub- 
sequent formation  of  the  phenyl  ether  deriv  tive. 

The  second  method  of  prep-ring  this  compound 
that  was  tried  was  one  described  by  Jones  and  Cookfld),  50  rrams  oi 


Phenol  ./ere  melted  on  a steam  b th,  - d to  the  warm  liquid  was  added 
with  vigorous  stirring  55  grams  of  molten  sodium  hydroxide.  Con- 
siderable charring  ensued  and  the  product  obtained  was  a black  mass. 
By  this  method,  Jones  and  Cook  obtained  a pure  white  product (14 ) , so 


■ 


■ 


' 


-e- 


two  further  attempts  were  made  to  obtain  such  a prodi  ct  bp  means  of 
this  method.  Bach  time  the  product  was  extremely  dark. 

The  third  method  which  was  tried  was  a slight 
variation  from  the  above  method,  but  produced  a very  satisfactory, 
creamy- white  product.  35  grams  of  sodium  hydroxide  were  powdered 

in  a-  mortar,  and  added  to  50  grams  of  molten  phenol  to  i s ad- 

ded about  ten  cc.  of  alcohol.  During  the  addition  of  the  hydroxide 
the  mixture  was  stirred  vigorously.  The  stirring  was  continued  un- 
til the  r>roduct  became  a very  stiff  paste.  It  was  then  removed  and 
ground  to  a powder  i r,  and  placed  in  a stoppered  flask  to 

keep.  By  this  method  of  procedure  very  little,  if  any,  e 
takes  place  and  a creamy-white  product  results. 

Totassium  phenolate  was  prepared  in  the  same 


manner. 


The  Preparation  of  B-nitro-cklor-benzene, 


P-nitro-chlor-benzene  was  prepared  by  nitrating 
94  grams  of  chlorbenzene  with  100  cc . of  fuming  nitric  acih  - The 
mixture  was  kept  at  a temperature  of  not  over  40°C.  when  all  the 
chlorbenzene  had  been  added  slowly  to  the  nitric  acid  through  a drop- 
ping funnel,  while  continuously  stirring  the  mixture,  it  was  pourred 
into  a large  volume  of  cold  water.  There  was  formed  a heavy  oily 
substance,  th::t  settled  to  the  bottom  of  the  vessel,  and  partially 
crystallized,  forming  a semisolid  mass.  The  crystals  of  p-nitro- 
chlorbenzeme  were  filtered  off  by  suction  and  dried.  The  total 
yield  of  the  para  compound  was  45  grams. 

A second  run  was  made  for  the  preparation  of 
this  compound,  closer  attention  being  paid  to  the  amounts  of  perw  and 


-7- 


ortlio  compounds  produced. 

108  gms,  chlorbenzene. 

150  cc . fuming  nitric  acid. 

G5  gms.  p-nitro-chlorbenzene. 

192  gms.  o-nitro-chlorbenzene. 

257  gms. 

265  gms.  Yield  in  percent  of  theory 

97.# 

In  the  second  run  no  crystallization  took  place 
upon  pourring  the  nitrated  mixture  into  cold  water,  so  the  mixture 
was  again  separated  hy  means  of  a separatory  funnel, and  washed  with 
a dilute  solution  of  sodium  hydroxide.  The  oily  material  was  then 
run  into  water  from  the  separatory  funnel  and  allowed  to  stand  for 
some  time.  Crystals  of  the  p-compound  formed  and  were  filtered  from 
the  heavy  oily  o-compound.  The  o-compound  was  then  placed  in  a 
flash  and  cooled  to  0°C.  with  an  ice  hath.  A few  crystals,  formed 
hy  freezing  a small  amount  of  the  oily  liquid  in  a test  tube,  were 
introduced  into  the  liquid  in  the  flash.  A rapid  growth  of  cry- 
stals ensued.  The  temperature  of  the  freezing  oily  liquid  was  14.89 

A third  run  was  made  in  an  attempt  to  obtain 
larger  yields  of  the  p-compound.  A glass  stirrer,  turned  hy  a smell 
electric  motor  was  employed  and  the  temperature  was  hept  constant  hy 
placing  the  nitrating  flash  in  a large  volume  of  running  cold  water, 
ho  better  results  were  obtained,  theyield  of  the  p-compound  being  only 
2 Ok 

The  p-nitro-chiorbenzene , prepared  as  above,  was 
used  in  the  early  part  of  the  worh  done  in  the  preparation  of  mono- 
nitro- diphenyl  ether,  but  later  on,  the  commercially  prepared  com- 
pound was  available,  as  well  as  p-nitro-brombensene , and  these  com- 
mercially prepared  compounds  were,  therefore,  used  in  the  later  worh. 


Ingredients  : 
Yield*. 

Total  Yield: 
Theoretical : 


-8- 


T'henolate  and  _ itro-Ghlorbenzene 


'-'he  -'-'c  A : a i ' - L 


uio-Titro-fiohenwl  Ather  from  Sodium 


100  grams  of  sodium  phenolate  we  re  dissolved  in 


100  grams  of  phenol  at  150°0.  The  resulting  mixture  was  a "black 
looking  fluid.  Into  this  black  fluid  was  introduced  50  grams  of 
p-nitro-chlorbenzene.  The  mixture  was  then  refluxed  for  21  hours. 

A heavy  black  tary  mass  was  evident  in  the  bottom  of  the  flask  at 
the  end  of  that  time.  The  solution  was  then  washed  with  dilute  sod- 
ium hydroxide  and  the  alkaline  solution  was  then  washed  with  ether, 
and  the  ether  pourred  off  the  top.  Considerable  difficulty  was  ex- 
perienced in  making  the  separation  of  the  two  1 yeas,  because  of  the 
dark  color  of  both.  The  ether  extract  was  evaporated  to  dryness  on 
the  steam  bath  and  a second  ether  extraction  of  the  dark  mass  was 
made.  The  ether  solution  was  then  pourred  into  a large  amount  of 
petroleum  ether.  A heavy  dark  liquid  settled  to  the  bottom  of  the 
mixture  in  a small  amount,  about  20cc.  This  dark  liquid  was  sep- 
arated out  by  means  of  a separatory  funnel  and  the  process  of  ether 
extraction  and  subsequent  pouring  into  petroleum  ether  repeated  sev- 
eral times.  The  liquid  was  finally  evaporated  to  dryness,  dissolved 
again  in  ether,  and  again  evaporated  to  dryness  on  the  steam  bath. 

The  remaining  mass  was  still  black,  but  there  was  evidence  of  the 
formation  of  crystals.  This  partially  crystalline  residue  was  again 
taken  up  in  ether  and  repeatedly  shaken  with  animal  charcoal.  The 
charcoal  was  filtered  off  and  the  resulting  filtrate  was  again  evap- 
orated to  a small  volume.  The  dark  crystals  that  resulted  were  filt. 
ered  off,  and  dried,  and  their  melting  point  determined.  They  melt- 
ed at  47°C. 


Several  runs  were  made  on  the  preparation  of  this 


-9- 


comoound.  J-I10  sodium  phenolate  and  the  p—nitro— chlorbenzene  wore 
mixed  together  in  equal  proportions,  both  with  and  without  phenol  as 
a solvent.  The  temperature  t6  which  they  were  subjected  was  also 
varied  from  10G°C.  to  150°C.f  and  the  le  gt  of  time  of  the  heating 
r/as  also  varied.  The  best  results  were  obtained  by  heating  the  two 
in  equal  proportions  upon  the  steam  bath  for  30  hours,  extracting  the 
product  with  ether,  and  crystallizing  from  alcohol.  The  highest 
field  obtained  by  this  method  was  55$.  The  product  from  the  first 
)rop  of  crystals  melted  at  58°C.  to  59°C.  That  of  the  second  crop 
melted  at  from  57.5°C.  to  58.5°C.,and  that  of  the  third  crop  from 
57°-.  to  58. 3oC . The  first  crop  of  crystals  was  a pale  yellow  col- 
or, and  the  other  two  crops  were  slightly  darker. 

In  preparing  the  mono-nitro-diphenyl  ether  by  the 
above  mentioned  method,  the  powdered  sodium  phenolate  and  p-nitro- 
chlorbensehe  were  tnoroughly  mixed  in  a 500cc.  round  bottom  flask 
to  wnich  an  upright  air  cooled  condenser  tube  was  attached,  and  the 
mixture  was  nsateci  on  the  steam  bath.  During  the  heating,  a large 
amount  of  long  needle-like  crystals  formed  at  the  neck  of  the  flask, 
ana  in  one  lower  end  or  the  condenser  tube.  Before  extracting  the 
1 eac  cion  pro ciuc  c witn  ether,  some  or  these  crystals  were  removed 
110,1  khe  u°p  0-  cne  flask,  and  their  melting  point  was  determined. 

It  was  found  in  three  of  the  runs  in  which  this  method  was  used  that 
the  sublime  crystals  melted  at  from  82°C.  to  85°C.  in  the  first, 

79 . 5°G . to  82°G.  in  the  second,  and  from  82.5oC.  to  83. °C,  in  the 
third.  T-nitro-chlorbenzene  has  a melting  point  of  85°C.t  so  it 
was  assumed  that  these  sublimed  crystals  were  nothing  but  crystals 
or  the  original  p-nitro-chlorbenzene  which  had  not  reacted.  This 
assumption  was  born  out  by  the  appearance  of  similar  phenomena  oc- 


S 


1 


-10- 

cur  ring  in  work  done  later  with  p-nitro-brombenzene . 

The  Preparation  of  Aono-Uitro-Uiohenvl  Ather  from  Potassium 
Phenolate'  1 E-I-Atro-Arombonzenc  ~ 

In  their  work  upon  mono-nitro  diphenyl  ethers, 
•Jones  and  Cook  employed  potassium  phenolate  and  p-nitro-brombenzene 
fl4),  and  they  claimed  to  have  been  able  to  obtain  yields  of  82/^  of 
the  theory,  and  a pure  white  crystaline  product.  Using  their  me- 
thod of  preparation,  the  writer  heated  50  grams  of  each  of  these 
two  compounds  together  in  a 250  cc . round  bottom  flask  for  twenty 
hours  on  a steam  bath.  At  the  end  of  this  time  the  needle  like  cry 
3 tala  which  had  formed  at  the  top  of  the  flask  were  removed,  and 
were  found  to  have  a melting  point  of  from  121°C.  to  124°C,  After 
the  heating  was  continued  for  foir  days,  the.  crystals  that  had  form- 
ed were  again  examined, and  these  v/e re  found  to  have  a melting  poinLt 
of  from  106°G.  to  118°C.  It  was  assumed  from  these  facts  that  the 
crystals  first  examined  were  nearly  pure  sublimed  crystals  of  p- 
nitro-brombenzene  which  had  not  yet  reacted.  This  was  in  accor- 
dance with  the  results  expected  from  the  previous  work  with  p-nitro- 
chlorbenzene.  The  fact  that  after  the  additional  heating,  the  cry- 
stals that  were  formed  at  the  top  of  the  flask  were  found  to  melt  at 
a lower  temperature  may  be  explained  by  the  very  probable  assumption 
that  these  latter  crystals  were  contaminated  with  the  lower  melting 
mono-nitro-diphenyl  ether  which  was  the  product  of  the  reacting  sub- 
stances. 

The  nitro- diphenyl  ether  was  extracted  from  the 
mass  with  ether  and  then  crystallized  from  alcohol.  The  product 
melted  at  from  48oC.  to  52°C. 


. 


-11- 


A second  run  v.ras  made  in  the  sane  manner  as 
the  first,  except  that  the  mixture  was  heated  for  only  18  hours  on 
the  steam  hath  and  2 hours  in  an  oil  hath  at  150°C.  The  yield  ob- 
tained was  47  grams  from  50  grams  of  p-nitro-brombenzene.  Therefore 
the  yield  was  88.6/0  of  the  theory.  The  product  melted  at  from  56°C. 
to  57oC.  In  all  subsequent  preparations  of  this  compound  according 
to  this  method  the  product  obtained  with  one  crystallization  from 
alcohol  was  very  light  yellow,  and  had  a melting  point  of  between 
56°C.  and  60°C. 

The  results  of  the  work  carried  out  in  the 
p repara  tion  of  the  mono e-nitro- diphenyl  ether  with  both  p-chlor  and 

b> 

Ur  brombenzene  have  lead  the  writer  to  believe  that  the  ssumption, 
made  by  Jones  and  Cook(l4),  that  the  sublimed  crystals  appearing  at 
the  top  of  the  flask  containing  the  reacting  substances  were  the  -pure 
mono-nitro-diphenyl  ether  was  erroneous,  and  that  such  crystals  are 
nothing  but  some  of  the  original  substance  employed  which  has  sublimec 
and  condensed  upon  the  cooler  portions  of  the  flask  without  reacting 
with  the  potassium  phenolate.  The  writer  also  believes  that  the 
true  melting  point  of  the  pure  mono-nitro-diphenyl  ether  is  not  123.5 
as  was  supposed  by  Jones  and  Cook,  but  that  it  is  very  close  to  61°6. 
as  it  was  found  to  be  by  Haeussermann  and  H.  Teichmann(l7 ) . 

The  writer  also  wishes  to  point  out  the  fact 
that  the  theoretical  percentage  of  nitrogen  in  mono-nitro-diphenyl 
ether  is  6.5/3  and  not  12.3/3  as  was  stated  by  Jones  and  Cook(l4),  and 
that  even  if  it  were,  the  fact  that  their  analysis  of  the  sublimed 
crystals  showed  a nitrogen  content  of  12.21/0  would  not  show  that  the  ; 
crystals  were  pure  mono-nitro-diphenyl  ether,  for  the  molecular 
weight  of  p-nitro-brombenzene  is  very  close  to  that  of  mono-nitro-di- 


- 12- 

phenyl  ether  and  its  percentage  content  of  nitrogen  is  also  very 
close  to  that  of  the  latter  compound,  being  6.8/*>. 

The  Preparation  of  liono-^mino-^inhenvl  -fther  from  Llono-  hitro- 
fi phenyl  ^ther. 

This  compound  was  prepared  according  to  the 
method  of  Jones  and  Cookfld).  In  working  with  75  grams  of  the  nitro 
compound  considerable  difficulty  was  experienced  in  the  de tinning  of 
the  solution  of  the  reduced  mixture.  *-s  carried  out,  250  cc.  of  al- 
cohol were  used  to  dissolve  75  grams  of  crude  mono -nitro -diphenyl 
ether  on  the  water  bath.  75  grams  of  tin  were  added  and  the  evolut- 
ion of  hydrogen  was  produced  by  the  slow  addition  of  100  cc.  of  hy- 
drochloric acid  through  a dropping  funnel.  The  mixture  was  refluxed 
for  several  hours  on  the  steam  bath.  The  solution  became  turbid, 
and  water  was  added  to  decrease  the  turbidity.  The  alcohol  was 
boiled  off,  and  part  of  the  water  evaporated.  A heavy  light  colored 
precipitate  of  the  amino-  compound  formed.  Some  of  this  precipitate 
was  removed  and  its  melting  point  determined  to  be  92°C.  to  94°C . 

A large  volume  of  water  was  added  to  dissolve  all  the  amino  compound 
and  the  solution  filtered.  The  large  amount  of  filtrate  was  evap- 
orated to  a small  volume  on  the  steam  bath,  and  allowed  to  cool. 
Shining  white  crystals  crystallized  from  the  solution.  These  had  a 
melting  point  of  95°C. 

In  order  to  obviate  the  difficulty  of  com- 
pletely de tinning  the  large  volume  of  solution,  it  was  decided  to 
make  the  reduction  with  iron  and  a small  amount  of  hydrochloric  acid. 
The  reduced  mixture  was  allowed  to  cool,  and  the  amino  compound  cry- 
stallized out.  The  excess  iron  and  the  crystalline  p>roduct  v/ere 


, 


-13- 


filtered  from  the  solution  and  sucked  dry  upon  the  suction  filter. 

The  amino  compound  was  extracted  with  ether,  and  crystallized  from 
alcohol.  fhe  product  was  slightly  colored,  aand  gave  a melting  point 
of  87°C. 

lii c Production  of  I-fhenoxo -Ihew\fL--rsonlo  -cid. 

In  order  to  prepare  this  compound  from  p- 
amino- diphenyl  ether  use  was  made  of  Bart’s  reaction  for  the  replace- 
ment of  the  diazonium  group  by  the  arsenic  acid  grouping.  fen  grams 
of  the  amino  compound  was  treated  with  8.5  cc . of  concentrated  hyd- 
rochloric acid,  and  the  hydrochloride  formed  dissolved  in  400  cc . of 
water.  3.1  grams  of  HaNOo  was  dissolved  in  25  cc . of  water,  and 
dropped  with  vigorous  stirring  into  the  ice  cold  solution  of  hydro- 
chloride. fhe  temperature  of  the  mixture  was  maintained  at  5°C . 
throughout  the  addition. 

^ solution  of  sodium  carbonate  was  made  up, 
containing  20  grams  of  the  salt,  and  to  this  were  added  12.8  grams  of 
arsenious  oxide.  fhe  solution  was  made  up  to  a volume  of  about  200 
cc.,  filtered,  end  coofed  to  10°G.  in  an  ice  bath.  To  this  clear 
solution  was  added  0,4  gram  of  copper  sulfate,  and  a green  curdy  pre- 
cipitate formed.  !o  this  alkaline  mixture  was  added  slowly  and  with 
stirring  the  cooled  solution  of  the  diazonium  salt  of  diphenyl  ether. 
Considerable  frothing  ensued,  the  froth  being  scraped  off  the  top  as 
it  rose  above  the  sides  of  the  beaker.  The  temperature  of  the  re- 
acting mixture  was  maintained  at  10°C.  When  the  entire  amount  of 
the  diazo  solution .had  been  added,  the  mixture  was  allowed  to  stand 
until  the  evolution  of  nitrogen  had  ceased.  The  copper  coupling 
reagent  was  then  filtered  from  the  solution,  and  the  clear  filtrate 


. 


-14- 


was  acidified  with  hydrochloric  acid,  and  allowed  to  stand, 
finely  divided  crystalline  precipitate  formed  after  a short  time. 
This  was  filtered  off  from  the  large  volume  of  liquid,  dried  upon 
a clay  plate,  and  several  attempts  were  made  to  ascertain  its  melt- 
ing point.  It  did  not  melt  below  300°C.  The  dried  powder  had  a 
light  brownish-yellow  color,  so  an  attempt  was  made  to  purify  it  by 
means  of  two  alcohol  crystallizations.  jx  lighter  colored  product 
was  obtained,  but  it  did  not  melt  below  500°^.  The  yield  was  only 
25 p of  the  theory. 

An  analysis  for  arsenic  was  made  upon  the  re- 
crystallized product.  Two  samples  showed  20.62y  ana  21.25 y re- 
spectively. The  theoretical  percentage  is  25.51/0.  The  light  col- 
ored product  obtained  was  evidently  quite  impure.  The  lack  of 
time  prevented  further  investigation  concerning  the  preparation  and 
properties  of  this  compound. 

Summary . 

1.  A satisfactory  method  has  been  devel- 
oped for  the  preparation  of  alkali  phenolates  from  phenol,  alco- 
hol, and  an  alkali  hydroxide. 

2.  In  the  preparation  of  p-nitro-chlorben- 
zene  under  ordinary  conditions  of  nitration,  the  para  compound  is 
obtained  in  much  smaller  quantities  than  the  ortho  compound.  Vig- 
orous stirring  and  the  maintaining  of  a uniformly  low  temperature 
does  not  increase  the  yield  of  the  para  compound. 

3.  Mono -nitro -diphenyl  ether  is  best  pre- 
pared from  potassium  phenolate  and  p-nitro-bromrbenzene.  The  sub- 
limed crystals  forming  at  the  top  of  the  flask  in  the  preparation  of 


' 


-15- 


this  compound  are  probably  not  pure  mono-nitro-diphenyl  ether  as 
Jones  and  C0ok  said  they  were f 14),  hut  are  merely  the  original  nitro 
oenzene  derivative.  also,  the  pure  product  probably  has  not  the 
melting  point  of  12a. o J.  us  stated  by  Jones  and  Cook,  but  has  a 
melting  point  very  close  to  61°C.  as  stated  by  Hauessermaim  and 
Deichmann f 17  ) . 

a • -ri  saving  in  time  is  realized  in  the  re- 
paration of  mono -amino -diphenyl  ether  if  an  iron  reduction  is  em-  o 
ployed  ratner  than  a reduction  with  tin  and  hydrochloric  acid. 

• -art  s reaction  for  the  replacement  of 
o.ie  diazo  group  with  the  arsonic  acid  group,  with  the  aid  of  a cop- 
per salt  as  a coupling  agent  is  applicable  to  arsonic  acid  deriva- 
tives of  the  diphenyl  ether  series. 


' 


Be for one  os . 

1.  Witt,  Berichte,  1909,42,2955. 

2.  Morgan,  Gilbert  1. : Organic  Compounds  of  arsenic  and 
antimony,  1918. 

5.  Bart’s  Reaction:  Eng.  '.  568,  1911, D,ui._  , 250264. 

4.  Jacobs,  Beidelberger , and  Bolf:  on  nitro  and  amino  aryl 
arsonic  acids:  J.O.C.  40,2,  1918,  - 1580-1590. 

5.  Ber.  44,5302,  1911. 

6.  Ibid.  47,  1006,  1316,  1914. 

7.  Benda:  J.Prakt .Chem.  95,  74-106,  1917. 

J.Chem.Soc.  112,1,  599-601. 

8.  Chem.  age  P.Y.  28,  590-1,  1920. 

9.  A.  Schmidt , H.Gr,  Heysler,  and  Bodebeul:  -nn.  421,  159-74 
1921. 

10.  littermann:  Piss.  Botich,  1911. 

11.  G.2.  Bobertson  and  J.  Stieglitz:  J. Am. Chem. Soc . 45,  179-81, 
1921. 

12.  J.Chem.Soc.  117,865-75,  1920. 

15.  Brit.  p.  142,947,  Feb . 20,1919 . 

14.  J.-mer.Chem. Soc . Vol.  58,  pt.2,  - .1545,  1916. 

15.  J. Indust,  and  Eng. Chem.  Sept.  1919, -.825.  Badische  1 Bochst. 

16.  Bart’s  Beaction:  D.B.P.  268172. 

17.  Kauessermann  and  Deichmann:  Ber.  49,  1446,  1896. 


